J. Aerosp. Technol. Manag., São José dos Campos, Vol.6, No 4, pp.389-394, Oct.-Dec., 2014

ABSTRACT: Maraging steels have low carbon content and are highly alloyed, having as main feature the ability to increase the mechanical strength after thermal aging. Therefore, the objective of this work is to analyze the effect of aging in a Co-free maraging steel, Fe – 0.014% C – 0.3% Mn – 3.9% Mo – 2.1% Cu – 0.19% Si – 11.8% Cr – 9.1% Ni – 1.0% Ti (wt), at different heat treatment times (10 min - 960 min) at constant temperature (550°C), after cold rolling up to 66% and 77% area reduction. Microstructures were analyzed by scanning electron microscopy (SEM - EDS) and mechanical properties by Vickers hardness measurements. The results showed a significant increase in the hardness of the material after aging heat treatment on the solution treated and deformed samples. The aging heat treatment which was harder about 650 HV was 550°C/60 min.

KEYWORDS: Maraging steel, Cold rolling, Hardness test Aging.

Microstructural Analysis of Co-Free Maraging Steel AgedAline Castilho Rodrigues1, Heide Heloise Bernardi1, Jorge Otubo2

INTRODUCTION

Maraging steel was developed in the 1950’s, to support the demand for a low density and temperature resistant steel (250°C – 300°C), for improving aircraft performance. This new material was created adding aluminum (Al) and titanium (Ti) in steel with nickel (Ni). In the 1960’s, cobalt (Co) and molybdenum (Mo) were added into the composition of maraging steels. Clarence George Bieber, in International Nickey Company, studied the addition of these elements in the alloy and concluded that there is a significant increasing in mechanical resistance (Lopes, 2007; Méndez, 2000). The classification of commercial maraging steels, according to the percentage of nickel, is: 18Ni (250), 18Ni (300) and 18Ni (350) (Lopes, 2007).

Maraging steel received this name due to two words: martensite and aging, which mean martensite aged. Low carbon and alloyed, the maraging steels are capable of increasing their mechanical resistance and hardness after aging heat treatments. The treated solution state has a martensitic structure with high ductility and toughness, and it can be modified after aging heat treatments (Cardoso et al., 2013a). Due to the ductility of martensite, the maraging steel allows cold mechanical forming, not requiring intermediate heat treatment. A mechanical processing technique that can be used in maraging steel is cold rolling.

During the cold rolling, plastic deformation and increase of hardness occur, therefore, there is an increasing of dislocation density and crystalline defects, hindering the movement between them. Due to the plastic deformation, there is an increase in tensile strength and yield point (Callister, 2012). On the other hand, these mechanical properties can also be improved by thermal aging, in which the formation of intermetallic precipitates occurs. In Table 1,the types of precipitates which may be formed

doi: 10.5028/jatm.v6i4.400

1.Faculdade de Tecnologia de São José dos Campos – São José dos Campos/SP – Brazil 2.Instituto Tecnológico de Aeronáutica – São José dos Campos/SP – Brazil

Author for correspondence: Aline Castilho Rodrigues – Faculdade de Tecnologia de São José dos Campos – FATEC Prof. Jessen Vidal | Av. Cesare Mansueto Giulio Lattes, s/n, São José dos Campos/SP | CEP: 12.247-014 – Brazil | Email: alinerodrigues_1@msn.com

Received: 08/02/2014 | Accepted: 09/30/2014

J. Aerosp. Technol. Manag., São José dos Campos, Vol.6, No 4, pp.389-394, Oct.-Dec., 2014

390Rodrigues, A.C., Bernardi, H.H. and Otubo, J.

on maraging steels, depending on the alloy composition, are shown (Padial et al., 2000).

Steel with martensitic structure, when subjected to a heat treatment at a constant temperature, suffers a growth of intermetallic precipitates uniformly in the matrix (Carvalho et al., 2013). The precipitate size is a contributing factor to the increased mechanical resistance of maraging steels. The smaller the precipitates and the more coherent with the matrix, the greater the hardness of the alloy, since there is less space between the particles; furthermore, they act as barriers to movement of dislocations (Padial et al., 2000).

The alloying elements of maraging steel, such as molybdenum, titanium, nickel, cobalt, aluminum, and others, have a great influence on the mechanical properties of this alloy, in other words, they are responsible by precipitates hardeners (Carvalho et al., 2013). However, recent studies (Hu et al., 2008; Leitner et al., 2011; Mahmoudi et al., 2011; Mahmudi et al., 2011; Nili-Ahmadabadi, 2008; Schnitzer et al., 2010; Sha et al., 2013) are being conducted in maraging steels without cobalt addition, in order to reduce the production costs of this alloy. Maraging steels are considered expensive due to their materials’ preparation and expensive alloy elements such as nickel and cobalt processes. The elimination of the cobalt content and the substitution of nickel by cheaper elements, such as manganese, has been studied. Cobalt is used only to minimize the solubility of molybdenum. In the case of maraging steel studied, this element was replaced by chrome, which besides

improving the hardenability increases the corrosion resistance (Nili-Ahmadabadi, 2008).

Maraging steels are mainly applied in the aeronautical, aerospace, nuclear and military industries, as they have great advantages such as good weldability, high strength, high yield strength, high fracture toughness, they support high working temperatures, have good machinability, good formability, among others, with great applicability matrices and tools (Lopes, 2007).

High-tensile steels such as 300M and SAE 4340 have extensive application in aeronautics and aerospace industry, being mainly applied in the manufacture of structural components (Zang et al., 2013; Boakye-Yiadom et al., 2014).

Maraging steels are being investigated because of the possibility of replacing the commercial alloy steels, 300M and 4340 for example, widely used in aeronautical industry (Carvalho et al., 2013). Thus, this study aims to examine the effect of aging heat treatment in non-commercial maraging steel (Co-free), in order to compare it to the 300M and 4340 steels.

EXPERIMENTAL

The maraging steel used in this work was produced by vacuum induction melting. The ingots was hot forged and then hot rolled until we obtained bars of 20x20 mm of dimension and chemical composition: Fe – 0.014% C – 0.3% Mn – 3.9% Mo – 2.1% Cu – 0.19% Si – 11.8% Cr – 9.1% Ni – 1.0% Ti (wt.%).

Its bar (20x20 mm) was separated into two parts resulting in two conditions:• Condition I (C-I): bar dimension of 20 x 20 x 10 mm;• Condition II (C-II): bars of 20 x 20 x 10 mm (~100 wt.),

remelted (1 remelt) on an arc furnace, resulting in an ingot dimension of 16x10x95 mm.

Both conditions (C-I and C-II) were solution treated at 1050°C during 1 hour, quenched in water at room temperature and then cold rolled to a plate of 3 mm in thickness, resulting in 66 and 77 % of area reduction (AR) for C-I and C-II, respectively. The deformed samples (AR = 66 and 77 %) were cut in several parts and each part was annealed at 550°C for different times, ranging from 10 to 960 min.

Microstructural characterization was performed using a Scanning Electron Microscope (SEM) VEGA 3 TESCAN model, equipped with an energy dispersive spectrometer system (EDS). Vickers hardness

Table 1. Precipitates hardeners formed during the aging of maraging steels (Padial et al., 2000).

Phase Crystalline Structure

Ni3Mo Orthorhombic

Ni3Ti Hexagonal ordered

Ni3V Hexagonal compact

Ni3W Orthorhombic

Fe2(Mo, Ti) Type hexagonal laves

FeMo Tetragonal

FeTi CsCl type cubic

Fe7Mo4 Hexagonal

R (Mo-Co-Cr) Hexagonal rhombic

X (Fe-Cr-Mo) Body-centered cubic

J. Aerosp. Technol. Manag., São José dos Campos, Vol.6, No 4, pp.389-394, Oct.-Dec., 2014

391Microstructural Analysis of Co-Free Maraging Steel Aged

testing was performed using a Future-Tech FM-7000 microindenter with a load of 200 g/15s, in which the results correspond to the mean of ten values taken on each specimen. The micrograph analyses and the Vickers’ hardness were undertaken in a longitudinal section of the samples (wire rolling direction).

RESULTS AND DISCUSSION

Figure 1 shows the hardness variation as a function of heat treatment time for maraging steel with AR’s = 66 and 77 %. For solution treated (C-I and C-II) and deformed samples, the hardness values are represented at zero time in Fig. 1.

Solution treated samples (C-I and C-II) showed average hardness values of 250 and 300 HV, respectively. Comparing the solution treated to the deformed condition, it is observed an increase around 50 % in average hardness values (HV66% = 425

and HV77% = 407), corresponding to the effect of work hardening. About thermal aging, there is a significant increase in hardness at relatively low heat treating times (Fig. 1). For both area reductions, increased hardness around 200 HV occurs with only 10 min thermal aging. He et al. (2002) observed that the heat treatment at 470°C performed in a maraging steel with 18%wt. Ni, after forging, has achieved a 90% increase in hardness, with only 15 min of aging.

In the detail of Fig. 1, it is observed that the maximum hardness is obtained at 550°C/60 min for both ARs. On the other hand, the thermal aging at 550°C exhibits a decrease in hardness values after 240 min for deformed sample with AR = 66%, whereas a decrease it is observed after 90 min to condition AR = 77%. Therefore, it can be said that in smaller ARs, there is an increase in aging time of the alloy, delaying the onset of overaging. Based on the average hardness values, the processing) in the matrix, resulting in a lath martensitic structure (Mahmoudi et al., 2011; Hu and Wang, 2012), as shown in Figs. 2a and 2b. Co-free maraging steel is stable up to 16 hours of aging at 550°C.

Har

dnes

s (H

V)

Time (min)

0 100 200 300 400 500 600 700 800 900 1000 1100100

150

200

250

300

350

400

450

500

550

600

650

700

Har

dnes

s (H

V)

Time (min)

AR = 66%

AR = 77%

550°C

0 20 40 60 80 100 120 140 160 180 200 220 240 260560

570

580

590

600

610

620

630

640

650

660

670

680

Figure 1. Annealing behavior of the maraging steel deformed with AR’s = 66% and 77%.

J. Aerosp. Technol. Manag., São José dos Campos, Vol.6, No 4, pp.389-394, Oct.-Dec., 2014

392Rodrigues, A.C., Bernardi, H.H. and Otubo, J.

Figure 2. Microstructures of maraging steel under the conditions (a); (b) solution treated; (c); (d) deformed; (e); (f) aging at 550°C/1h (SEM-BSE) and (g); (h) aging at 550°C/16h (SEM-SE).

(a)

(c)

(e)

(g)

(b)

(d)

(f)

(h)

AR = 66% 20 μm

AR = 66% 20 μm

AR = 66% 20 μm

AR = 66%

P2 P3

Matrix

P5

Matrix

5 μm

AR = 77% 20 μm

AR = 77% 20 μm

AR = 77% 20 μm

AR = 77% 5 μm

J. Aerosp. Technol. Manag., São José dos Campos, Vol.6, No 4, pp.389-394, Oct.-Dec., 2014

393Microstructural Analysis of Co-Free Maraging Steel Aged

Table 2. Chemical compositions of the constituent phases (wt.%).

Constituent Mo Ti Ni Cr

Composition 3.9 1.0 9.1 11.8

Matrix 1 4.6 1.2 9.2 12.1

Precipitate 2 (P2) 16.0 3.0 4.7 14.1

Precipitate 3 (P3) 7.6 12.5 6.4 9.9

Matrix 4 4.5 1.0 9.0 12.5

Precipitate 5 (P5) 14.5 2.6 5.4 14.8

Figure 2 shows the microstructure of the maraging steel at different conditions. It is observed for solution treated sample (C-I and C-II) that the solution heat treatment at 1050°C for 1h was effective in dissolving primary precipitates (formed during the early stages of maraging steel

After thermal aging at 550°C for 1 hour (Figs. 2e and 2f), it can be seen that the microstructure is similar to deformed samples in AR = 66 and 77 % (Figs. 2c and 2d). This heat treatment time showed to be effective in relation to increased hardness (Fig. 1), due to presence of fine precipitates dispersed in the matrix, which contribute to the increase of this mechanical property (Hu and Wang, 2012). However, the technique of scanning electron microscopy, used in order to analyze the microstructure of this alloy, is not efficient to identify them in the matrix.

Increasing the annealing time to 16 h (Figures 2g and 2h) promoted an increment in precipitation rate. These precipitates grew coarser in subsequent higher annealing times, but there still are fine precipitates elongated in the rolling direction, and few precipitates changed from elongate morphology to a spherical one. In this condition, it is observed some coalescence of precipitates having sizes of the order of 2 μm. Regardless of AR, the precipitates have similar morphologies. The EDS analysis (Table 2) showed that those precipitates, referred as P2 and P5, were depleted in Ni, and enriched in Mo and Ti (Figures 2g and 2h).

In the analysis performed on the matrix — points 1 and 4 in Figs. 2g and 2h, respectively —, compared to the nominal composition of the alloy, it can be said that the rolling processes or thermal treatments did not significantly alter the composition of the material in terms of Mo, Ti, Cr and Ni elements.

In relation to precipitates P2 and P5, a large increase of Mo and Ti was observed. This alloy contains low nickel, so it is not possible to stimulate the formation of Ni3Mo or Ni3Ti phases, which usually appear in the commercial maraging steels 250 and 350 (Padial et al., 2000). The presence of cobalt element in commercial alloys promotes the formation of Ni3Mo. On the other hand, the maraging steel study in this work does not have Co (Co-free) and low Ni content. However, the alloy phase formed in this alloy can be Fe2(Mo, Ti), FeMo, FeTi or Fe7Mo4 (Padial et al., 2000). The precipitate P3 features a larger enrichment of Ti in relation to P2 and P5, probably, the Ti-rich precipitates are carbides (TiC) or Fe2Ti, FeTi (Castanheira et al., 2006). The TiC is formed by carbon, which is characterized as

an impurity of the material (Padial et al., 2000). Furthermore, other techniques are necessary, for example, an X-ray diffraction to determine the type of precipitate formed.

The SAE 4340 and 300M steels are considered high-tensile steels, low-carbon and low-alloy steels, being used in the aerospace industry due to their excellent mechanical properties. Commercial maraging steels are being studied in order to replace the 4340 and 300M steels, especially in the aeronautical and aerospace industry. According to studies by Cardoso et al. (2013b), the SAE 4340 and 300M steels can achieve hardness values of 250 HV and 350 HV, respectively, after drawing back. However, the maraging steel studied with forming processes and appropriate heat treatment can achieve hardness values around 670 HV, i.e., almost double the amount reported by the 300M steel.

CONCLUSION

Based on this investigation, the following conclusions can be drawn:• The cold forming contributes to mechanical hardening,

however an effective increase of hardness is obtained after thermal aging;

• The hardness increased significantly with low time thermal aging at 550°C due to precipitation of the second phase particles. The maximum value obtained was of 650 HV at 550°C/60 min;

• Based on the average hardness values, the Co-free maraging steel is stable for up to 16 hours of aging at

J. Aerosp. Technol. Manag., São José dos Campos, Vol.6, No 4, pp.389-394, Oct.-Dec., 2014

394Rodrigues, A.C., Bernardi, H.H. and Otubo, J.

550°C. It is possible to note a subtle decrease in the hardness values for both AR, due to coarsening of precipitates;

• Appropriate thermal aging promoted the precipitation of the second phase particles, rich in Mo and Ti.

ACKNOWLEDGEMENTS

The authors are thankful to FAPESP, CNPq, CNPq Universal (476030/2011-0), DCTA/IEAv, Villares Metals SA and Multialloy-Metais e Ligas Especiais Ltda.

REFERENCESBoakye-Yiadom, S., Khan, A.K. and Bassim, N., 2014, “A systematic study of grain refinement during impact of 4340 steel”, Materials Science and Engineering: A, Vol. 605, pp. 270-285. doi: 10.1016/j.msea. 2014.03.066.

Callister, W.D.Jr., 2012, “Fundamentos da Ciência e Engenharia de Materiais: uma abordagem integrada”, Rio de Janeiro: Editora LTC.

Cardoso, A.S.M., Abdalla, A.J., Lima, M.S.F., Bonjorni, F.M., Barbosa, M.J.R., Baptista, C.A.R.P. and Fanton, L., 2013a, “Study of Laser Welding and Heat Treatments Done in Different High Strength Steels: 4340, 300M, Maraging 300”, SAE Technical Paper Series, Vol. 36, pp. 1-5. doi:10.4271/2013-36-0510.

Cardoso, A.S.M., Abdalla, A.J., Ueda, M., Lima, M.S.P. and Bonjorni, F.M., 2013b, “Microstructural Characterization of the 4340 and 300M Steels After Laser Welding, Heat Treatment and Surface Plasma”, In: SAE, São Paulo.

Carvalho, L.G., Andrade, M.S., Plaut, R.L., Souza, F.M. and Padilha, A.F., 2013, “A dilatometric study of the phase transformations in 300 and 350 maraging steels during continuous heating rates”, Materials Research, Vol. 16, No. 4, pp. 740-744. doi: 10.1590/S1516-14392013005000069.

Castanheira, M., Tikhomirov, V.V., Ozerskiy, A.D., Da Silva, J.E.R. and Lucki, G., 2006, “Influência dos Elementos de Liga e do Tratamento Térmico na Estrutura e Propriedades Mecânicas de um Aço Maraging sem Cobalto Resistente à Corrosão”, Anais do 17º CBECIMat, Brasil.

He, Y., Yang, K., Qu, W., Kong, F. and Su, G., 2002, “Strengthening and toughening of a 2800-MPa grade maraging steel”. Materials Letters, Vol. 56, No. 5, pp. 763-769. doi: 10.1016/S0167-577X(02)00610-9.

Hu, Z.F., Mo, D.F., Wang, C.X., He, G.Q. and Chen, S.C., 2008, “Different behavior in electron beam welding of 18Ni Co-free maraging steels”. Journal of Materials Engineering and Performance, Vol. 17, No. 5, pp. 767-771. doi: 10.1007/s11665-007-9190-4.

Hu, Z.F. and Wang, C., 2012, “Effect of Tube Spinning With Subsequent Heat-Treatment on Performance and Microstructure Evolution of T250 Maraging Steel”. Journal of Iron and Steel Research International, Vol. 19, No. 5, pp. 63-68. doi:  10.1016/S1006-706X(12)60101-0.

Leitner, H., Schober, M., Schnitzer, R. and Zinner, S., 2011, “Strengthening behavior of Fe-Cr-Ni-Al-(Ti) maraging steels”. Materials Science and Engineering: A, Vol. 528, No. 15, pp. 5264-5270. doi: 10.1016/j.msea.2011.03.058.

Lopes, J.C.O., 2007, “Os aços Maraging”. Ciência e Tecnologia dos Materiais, Vol. 19, No 1-2, pp. 41-44.

Mahmudi, A., Nedjad, S.H. and Behnam, M.M.J., 2011, “Effects of cold rolling on the microstructure and mechanical properties of Fe-Ni-Mn-Mo-Ti-Cr maraging steels”. International Journal of Minerals, Metallurgy and Materials, Vol. 18, No 5, pp. 557-561. doi: 10.1007/s12613-011-0477-y.

Mahmoudi, A., Ghavidel, M.R.Z., Nedjad, S.H., Heidarzadeh, A. and Ahmadabadi, M.N., 2011, “Aging behavior and mechanical properties of maraging steels in the presence of submicrocrystalline Laves phase particles”. Materials Characterization, Vol. 62, No. 10, pp. 976-981. doi: 10.1016/j.matchar.2011.07.012.

Méndez, D., 2000, “Una revisión de los aceros Maraging”, Revista Ciência Abierta, No. 28, Chile.

Nili-Ahmadabadi, M., 2008, “Improvement in mechanical properties of Fe-Ni-Mn maraging steel by heavy cold rolling”. International Journal of Modern Physics B, Vol. 22, No 18-19, pp. 2814-2822. doi: 10.1142/S0217979208047638.

Padial, A.G.F., Monteiro, W.A., Andrade, A.H.P. and Rigo, O.D., 2000, “Microstrutural Analysis os 400 grade Maraging Steel After Thermomechanical Treatment”. Thermec 2000, Estados Unidos.

Schnitzer, R., Schober, M., Zinner, S. and Leitner, H., 2010, “Effect of Cu on the evolution of precipitation in an Fe-Cr-Ni-Al-Ti maraging steel”, Acta Materialia, Vol. 58, No. 10, pp. 3733-3741. doi: 10.1016/j.actamat.2010.03.010.

Sha, W., Chen, Z., Geriletu, X.X.X., Lee, J.S., Malinov, S. and Wilson, E.A., 2013, “Tensile and impact properties of low nickel maraging steel”. Materials Science and Engineering: A, Vol. 587, pp. 301-303. doi: 10.1016/j.msea.2013.08.076.

Zang, G., Yang, X., He, X., Li, J. and Hu, H., 2013, “Enhancement of mechanical properties and failure mechanism of electron beam welded 300M ultrahigh strength steel joints”. Materials and Design, Vol. 45, pp. 56-66. doi: 10.1016/j.matdes.2012.09.004.